CN106179501A - A kind of polyamic acid carried metal nanocatalyst and preparation method thereof - Google Patents
A kind of polyamic acid carried metal nanocatalyst and preparation method thereof Download PDFInfo
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- CN106179501A CN106179501A CN201610511406.5A CN201610511406A CN106179501A CN 106179501 A CN106179501 A CN 106179501A CN 201610511406 A CN201610511406 A CN 201610511406A CN 106179501 A CN106179501 A CN 106179501A
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- polyamic acid
- metal
- acid
- solution
- nanocatalyst
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- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 65
- 239000002184 metal Substances 0.000 title claims abstract description 65
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 38
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000012279 sodium borohydride Substances 0.000 claims description 15
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000004952 Polyamide Substances 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 229920002647 polyamide Polymers 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- -1 silver tetrafluoroborate Chemical compound 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229910021608 Silver(I) fluoride Inorganic materials 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 2
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 20
- 239000002082 metal nanoparticle Substances 0.000 abstract description 17
- 238000006722 reduction reaction Methods 0.000 abstract description 12
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 3
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007172 homogeneous catalysis Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000004936 stimulating effect Effects 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008876 conformational transition Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/27—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a liquid or molten state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/17—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/18—Gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of polyamic acid carried metal nanocatalyst and preparation method thereof.Prepare high dispersion metal nanoparticle with polyamic acid for carrier, and use as catalyst.The present invention, by being mixed with slaine by water-soluble polyamic acid salt solution, obtains the complex of polyamic acid and metal ion, then is reacted with reducing agent by this complex, obtains the metal nano catalyst of polyamic acid load.Load type metal nanocatalyst good stability prepared by the inventive method, dispersibility is high, and has the sensitive water dispersible of pH.Described catalyst has high-efficiency catalytic activity and reusing to the reduction reaction of paranitrophenol.
Description
Technical field
The invention belongs to metal nano catalyst preparation technical field, be specifically related to a kind of accurate homogeneous, recyclable and repeat
Metal nano catalyst utilized and preparation method thereof, particularly relates to a kind of with water-soluble polyamic acid salt as carrier, with metal
Salt is metal precursor, uses chemical reduction method, the method preparing the load type metal nanocatalyst of quasi-homodisperse.
Background technology
The superhigh specific surface area that metal nanoparticle has, the activity strong to reactant, and huge physical chemistry
Modify space, make them increasingly come into one's own in catalyst field.Be usually used in the metal of catalyst field have silver, gold, palladium and
The noble metals such as platinum.However, it is contemplated that Precious Metals Resources is limited, and in order to give full play to the high catalysis of metal nano catalyst
Activity, it is generally required to metal nanoparticle to be carried on suitable carrier, thus keep metal nanoparticle high dispersion state and
Repeatable usability.Therefore, the novel carriers material of exploitation catalyst, and set up metal nano catalyst payload side
Method, is the important topic of high performance catalyst research.
Stimulating responsive macromolecule is that a class is along with the change meeting of ambient parameters (such as temperature, pH, ion concentration etc.)
There is the macromolecule of reversible conformation transition.When as the carrier of metal nano catalyst, stimulating responsive high molecular certain
A little physically or chemically sensitivity (such as dissolubility, volume, shape, specific surface area and mechanical performances etc.), can be to its carried metal
Some performance of nanocatalyst plays regulatory role.Polyamic acid is a kind of containing a large amount of carboxyls with amide groups active function groups
Macromolecule, has stronger complexing to metal, and therefore water-soluble polyamic acid solution is to prepare high dispersion metal in situ to receive
The good medium system of rice corpuscles.(Synthesis of silver nanocubes with controlled size
using water-soluble poly(amic acid)salt as the intermediate via a novel ion-
Exchange self-assembly technique, Nanoscale, 2013,5,12,132 12135) additionally, polyamic acid is
A kind of stimulating responsive macromolecule, has significant pH sensitivity, can give metal nano catalyst more rich functional (as
Adjustable water dispersible and micro-reaction environment etc.) so that it is the more efficient and intelligent (Poly (amic acid) of catalytic performance
salt-stabilized silver nanoparticles as efficient and recyclable quasi-
homogeneous catalysts for the aqueous hydration of nitriles to amides,New
Journal of Chemistry,2016,40(1),358–364).Up to the present, only 1 document is reported with polyamic acid
Prepare metal nano catalyst for carrier, but its carried metal kind is only limitted to silver, to widely metal nano catalyst
Load there is not yet document report.
Summary of the invention
It is contemplated that overcome the deficiencies in the prior art, it is provided that a kind of polyamic acid carried metal nanocatalyst and system thereof
Preparation Method.
In order to achieve the above object, the technical scheme that the present invention provides is:
In described polyamic acid carried metal nanocatalyst, the molal quantity of metal ion is polyamic acid carboxyl molal quantity
0.1 20 times, preferably 2 times.Wherein, the physical characteristic parameter of described polyamic acid carried metal nanocatalyst is: gold
Genus nanoparticle is near-spherical, and mean diameter is 1 20nm；Chemical feature parameter is: metal nanoparticle is zero-valent state, polyamides
Containing a large amount of carboxyls and amide groups in amino acid molecular structure.
The preparation method of described polyamic acid carried metal nanocatalyst comprises the steps:
(1) water-soluble polyamic acid salt is dissolved in deionized water, is configured to the polyamide that concentration is 0.013-1.3wt%
Acid salt aqueous solution；
(2) in polyamic acid saline solution, add metal salt solution, stir under room temperature, obtain metal ion with poly-
The complex solution of amic acid；
(3) complex solution obtained in step (2) is reacted with sodium borohydride or hydrazine hydrate, obtain polyamic acid load
Metal nano catalyst dispersion；
(4) being 25 with the metal nano dispersion liquid pH value obtained in acid-base modifier regulating step (3), polyamic acid is born
The metal nano catalyst carried settles, and by crossing cleaner liquid, removes various water-solubility impurity ions in dispersion liquid, collects
Metal nano catalyst sedimentation thing rejoin again in the acid-base modifier that pH value is 7 12 and heavily disperseed, and finally
Return to the polyamic acid carried metal nanocatalyst of quasi-homodisperse state.
Wherein, step (1) described water-soluble polyamic acid salt is by polyamic acid and amine (such as triethylamine, piperidines etc.), alcohol
Amine (such as triethanolamine, N methyldiethanol amine, diethanolamine, ethanolamine etc.), quaternary ammonium bases are (such as Tetramethylammonium hydroxide
Deng) reacting prepared, polyamic acid is obtained by polycondensation reaction well known to those skilled in the art, including any one or more of diamidogen
The polyamic acid obtained with any one or more of dianhydride polycondensation.As diamidogen can be 4,4 '-diaminodiphenyl ether (ODA),
Phenylenediamine (m-PDA), p-phenylenediamine (p-PDA) etc.；Dianhydride can be pyromellitic acid dianhydride (PMDA), 3,3 ', 4,4 '-benzophenone
Tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-two methyl phenyl ethers anisole tetracarboxylic dianhydrides (ODPA) etc..
Step (2) described metal salt solution is silver nitrate, silver acetate, silver ammino solution, Argentous fluoride, silver tetrafluoroborate, chlorine gold
In acid, sodium chloraurate, potassium chloroaurate, chlorine palladium acid sodium, potassium chloropalladate, chloroplatinic acid, platinic sodium chloride, potassium chloroplatinate aqueous solution one
Kind.It is preferably the one in silver nitrate, gold chloride, chlorine palladium acid sodium, platinic sodium chloride aqueous solution.
During step (3) described complex solution reacts with sodium borohydride or hydrazine hydrate, the slaine in complex solution with
The mol ratio of sodium borohydride or hydrazine hydrate is 1:(0.5 20), preferably 1:(1 2), reaction temperature is-5 100 DEG C, preferably
Being 0 DEG C, the response time is 0.5 24h, preferably 2h.
Step (4) described acid-base modifier is hydrochloric acid, acetic acid, triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate or carbon
Acid potassium.It is preferably acetic acid and sodium hydroxide.
Polyamic acid carried metal nanocatalyst of the present invention can be used for preparing chemical reaction catalyst.
In the present invention, the preparation principle of catalyst is as follows:
In polyamic acid saline solution, the preparation process of metal nanoparticle mainly experiences 2 stages, as shown in Figure 8: a)
Metal ion (Mn+) and polyamic acid salt (PAAS) complexation, form metal macromole (PAA M N) complex；B) metal-divide greatly
Sub-complex is reduced agent reduction, and under the Stabilization of polyamic acid salt, and forming core and grow into metal nanoparticle
(MNPs), thus obtain polyamic acid load metal nano catalyst.The final size of metal nanoparticle, shape and dispersion
State is relevant with the kind of polyamic acid salt, the consumption of slaine, the consumption of reducing agent, reduction reaction temperature etc..
The metal nano catalyst of polyamic acid of the present invention load can be catalyzed reduction paranitrophenol (4-NP) reaction
For model reaction.By 4-NP by sodium borohydride (NaBH4) reaction rate that is reduced into para-aminophenol (4-AP) evaluates
State the catalysis activity of metal nano catalyst, and by regulation reacting solution pH value, make metal nano catalyst realize convenient
Recycle and reuse.
In order to contrast the activity difference of different catalysts, the catalytic reaction condition being used uniformly across is: the concentration of 4-NP is
0.1mM, NaBH4Concentration be 10mM, the concentration of metal nano catalyst is 0.1 10 μMs.The reaction time used is 5 60 points
Clock.
Identical with catalyst preparation step (4), can be by heavy for the acid of metal nano catalyst after catalytic reaction completes
Fall, it is achieved the recovery of metal nano catalyst, the metal nano catalyst of recovery can heavily disperse in alkaline aqueous solution, and use
In the quasi-homogeneous catalysis of next round.For the ease of operation, the reduction reaction scale of 4-NP is amplified, uses following catalytic reaction
It is 0.05M, NaBH that condition evaluates the recovery of catalyst with the concentration of repetition catalytic effect: 4-NP4Concentration be 0.25M, gold
The concentration belonging to nanocatalyst is 2.5mM.The reaction time used is 10min 2h.
In the present invention, the application principle of catalyst is as follows:
The metal nano catalyst of polyamic acid load has pH sensitivity in aqueous phase, and this is due to polyamic acid molecule
Containing a large amount of active group carboxyls in structure.On the one hand, carboxyl has good complexing, a side to metal nanoparticle
Face, carboxyl has weakly ionized effect, sensitive to pH value of solution.The carboxyl release proton of polyamic acid in neutral and alkaline conditions,
It is ionized into polyamic acid salt, thus metal nanoparticle is played good peptizaiton, to realize efficient quasi-homogeneous catalysis.
Along with solution acidic strengthens, polyamic acid protonation increases, and the macromolecular chain originally unfolded gradually is rolled up, by metal nano
Particle tight, so that metal nanoparticle separates out from solution, simple filtration can realize returning of metal nano catalyst
Receive.The metal nano catalyst reclaimed heavily can disperse in alkaline aqueous solution, and for the quasi-homogeneous catalysis of next round, such as Fig. 9
Shown in.
Compared with prior art, the present invention has a following superiority:
1) the inventive method is simple to operate, is suitable for being prepared on a large scale.
2) the inventive method is applicable to the preparation of various metal nano catalyst, and the metal nanoparticle size of preparation can
With the least (< 5nm), monodispersity is high.
3) the metal nano catalyst prepared by the inventive method has pH sensitivity, can be effectively used for metal nano catalysis
The purification of agent, accurate homogeneous efficient catalytic, recycle and reuse.
4) the inventive method is with water as solvent, environment friendly and pollution-free.
In a word, the present invention prepares high dispersion metal nanoparticle with polyamic acid for carrier, and comes as catalyst
Use.The present invention, by being mixed with slaine by water-soluble polyamic acid salt solution, obtains the network of polyamic acid and metal ion
Compound, then this complex is reacted with reducing agent, obtain the metal nano catalyst of polyamic acid load.Prepared by the inventive method
Load type metal nanocatalyst good stability, dispersibility is high, and has the sensitive water dispersible of pH.Described catalyst is to right
The reduction reaction of nitrophenol has high-efficiency catalytic activity and reusing.
Accompanying drawing explanation
With PMDA/ODA based polyamide hydrochlorate as carrier in Fig. 1: embodiment 1, the presoma being silver with silver nitrate, prepared
The TEM image of Nano silver grain；
With BTDA/ODA based polyamide hydrochlorate as carrier in Fig. 2: embodiment 2, the presoma being gold with sodium chloraurate, prepare
The TEM image of golden nanometer particle；
With ODPA/p-PDA based polyamide hydrochlorate as carrier in Fig. 3: embodiment 3, the presoma with platinic sodium chloride as platinum, system
The TEM image of the nano platinum particle obtained；
With BTDA/m-PDA based polyamide hydrochlorate as carrier in Fig. 4: embodiment 4, the presoma with chlorine palladium acid sodium as palladium, system
The TEM image of the Pd nano particle obtained；
Fig. 5: under different solutions pH value, the Zeta potential of the Nano silver grain of polyamic acid salt load is measured；
Fig. 6: the TEM image of the scattered golden nanometer particle of weight；
During the palladium nanocatalyst catalysis paranitrophenol reduction reaction of Fig. 7: polyamic acid salt load, along with reaction
The uv-visible absorption spectroscopy change curve extending reaction solution of time；
Fig. 8: the preparation process of metal nanoparticle in polyamic acid saline solution；
The application principle of the palladium nanocatalyst of Fig. 9: polyamic acid salt load.
Detailed description of the invention
The raw material used in the embodiment of the present invention is commercially available.
Embodiment 1
The PMDA/ODA based polyamide triethylenetetraminehexaacetic acid amine salt dry silk taking 0.13g is dissolved in 100mL deionized water, stirring and dissolving
After, adding 10mL concentration is the silver nitrate solution of 0.1M, after stirring, is cooled to 0 DEG C, and rapidly joining 10mL concentration is 0.1M
Sodium borohydride solution, continue stirring 2 hours, obtain the silver nanoparticle catalyst of polyamic acid salt load, accurate all for reddish brown
Phase solution, altogether 120mL.
Embodiment 2
The BTDA/ODA based polyamide triethylenetetraminehexaacetic acid alcohol amine salt dry silk taking 0.13g is dissolved in 100mL deionized water, stirs molten
Xie Hou, adding 10mL concentration is the chlorauric acid solution of 0.01M, after stirring, is cooled to 0 DEG C, and rapidly joining 2mL concentration is
The sodium borohydride solution of 0.1M, continues stirring 2 hours, obtains the gold nano catalyst of polyamic acid salt load, for rose
Quasi-homogeneous phase solution, altogether 112mL.
Embodiment 3
The ODPA/p-PDA based polyamide triethylenetetraminehexaacetic acid amine salt dry silk taking 0.13g is dissolved in 100mL deionized water, stirs molten
Xie Hou, adds the platinic sodium chloride solution that 10mL concentration is 0.01M, after stirring, is cooled to 0 DEG C, and rapidly joining 2mL concentration is
The sodium borohydride solution of 0.1M, continues stirring 2 hours, obtains the platinum nano catalyst of polyamic acid salt load, accurate for light black
Homogeneous phase solution, altogether 112mL.
Embodiment 4
The BTDA/m-PDA based polyamide triethylenetetraminehexaacetic acid alcohol amine salt dry silk taking 0.13g is dissolved in 100mL deionized water, stirring
After dissolving, add the chlorine palladium acid sodium solution that 10mL concentration is 0.01M, after stirring, it is cooled to 0 DEG C, adding 2mL concentration is
The sodium borohydride solution of 0.1M, continues stirring 2 hours, obtains the palladium nano-catalytic agent solution of polyamic acid salt load, for pitch black
The quasi-homogeneous phase solution of color, altogether 112mL.
The catalytically active assessment of the palladium nanocatalyst of embodiment 5 BTDA/ODA based polyamide triethylenetetraminehexaacetic acid alcohol amine salt load
As a example by the palladium nanocatalyst of the BTDA/ODA based polyamide triethylenetetraminehexaacetic acid alcohol amine salt load prepared by embodiment 4
Study its catalysis activity: the palladium nano-catalytic agent solution loaded by a certain amount of polyamic acid salt is through suitable dilution, then
Join in the cuvette of 1cm specification, be separately added into a certain amount of deionized water subsequently, 1mL concentration is the NaBH of 30mM4Solution
4-NP solution (keeping reaction solution cumulative volume is 3mL) with 30 μ L concentration are 10mM, the most quickly stirs and puts into purple
In the photometric sample cell of outer visible ray.Recorded by the absorbing state measuring reactant 4-NP and product 4-AP in real time and urge
Change the progress of reaction, as shown in Figure 7.
Table 1 lists what 4-NP reduction reaction was catalyzed by the various standards homogeneous nano metal nanoparticle reported in recent years
Effect.By contrast, we have affirmed that 4-NP reduction reaction is had by the accurate homogeneous metal nano catalyst that polyamic acid loads
Than many accurate homogeneous metal nano catalyst higher catalysis activity.
The catalysis activity of 4-NP reduction reaction is contrasted by the homogeneous metal nanoparticle of the various standard of table 1
Embodiment 6 PMDA/ODA based polyamide triethylenetetraminehexaacetic acid amine salt load silver nanoparticle catalyst recovery with repeat catalysis
Effect assessment: (concentration of 4-NP is 0.05M, NaBH4Concentration be 0.25M, the concentration of metal nano catalyst is 2.5mM.Instead
Should the time used be 10min 2h.) by 0.5mmol 4-NP and 2.5mmol NaBH4It is added separately to 7.5mL deionized water
In, subsequently under room temperature and argon atmosphere, add the silver nanoparticle catalyst solution that 2.5mL concentration is 10mM, and be stirred vigorously anti-
Should.After reaction terminates, with the acetic acid regulation reaction solution of 1M to pH～3, and reaction solution is stood a moment, treat that catalyst is complete
After sedimentation, use and directly topple over or the method for low-speed centrifugal (5000rpm, 10min), the catalysis that polyamic acid can be loaded
Agent separates with clear liquid.The catalyst reclaimed joins in 2.5mL water, adjusts pH to 8 by the NaOH solution of 1M, makes catalyst heavily divide
Dissipate, i.e. can be directly used for being catalyzed next time.(the results are shown in Table 2).
The repetition catalytic effect of the silver nanoparticle catalyst paranitrophenol reduction reaction of table 2 polyamic acid salt load
Claims (9)
1. a polyamic acid carried metal nanocatalyst, it is characterised in that described polyamic acid carried metal nano-catalytic
In agent, the molal quantity of metal ion is 0.1 20 times of polyamic acid carboxyl molal quantity.
2. polyamic acid carried metal nanocatalyst as claimed in claim 1, it is characterised in that described polyamic acid loads
In metal nano catalyst, the molal quantity of metal ion is 2 times of polyamic acid carboxyl molal quantity.
3. the preparation method of polyamic acid carried metal nanocatalyst described in claim 1 or 2, described method includes walking as follows
Rapid:
(1) water-soluble polyamic acid salt is dissolved in deionized water, is configured to the polyamic acid salt that concentration is 0.013-1.3wt%
Aqueous solution；
(2) in polyamic acid saline solution, add metal salt solution, stir under room temperature, obtain metal ion and polyamide
The complex solution of acid；
(3) complex solution obtained in step (2) is reacted with sodium borohydride or hydrazine hydrate, obtain the gold of polyamic acid load
Belong to nano-catalytic agent dispersing liquid；
(4) it is 25 with the metal nano dispersion liquid pH value obtained in acid-base modifier regulating step (3), polyamic acid load
Metal nano catalyst settles, and by crossing cleaner liquid, removes various water-solubility impurity ions in dispersion liquid, the gold collected
Genus nanocatalyst precipitum rejoins in the acid-base modifier that pH value is 7 12 again and is heavily disperseed, and finally recovers
Polyamic acid carried metal nanocatalyst to quasi-homodisperse state.
4. method as claimed in claim 3, it is characterised in that step (1) described water-soluble polyamic acid salt is by polyamic acid
Prepare with amine, alcamines, the reaction of quaternary ammonium bases.
5. method as claimed in claim 4, it is characterised in that step (2) described metal salt solution be silver nitrate, silver acetate,
Silver ammino solution, Argentous fluoride, silver tetrafluoroborate, gold chloride, sodium chloraurate, potassium chloroaurate, chlorine palladium acid sodium, potassium chloropalladate, chloroplatinic acid,
One in platinic sodium chloride, potassium chloroplatinate aqueous solution.
6. method as claimed in claim 5, it is characterised in that step (2) described metal salt solution be silver nitrate, gold chloride,
One in chlorine palladium acid sodium, platinic sodium chloride aqueous solution.
7. method as claimed in claim 3, it is characterised in that step (3) described complex solution and sodium borohydride or hydration
In hydrazine reaction, the slaine in complex solution is 1:(0.5 20 with the mol ratio of sodium borohydride or hydrazine hydrate), reaction temperature
For-5 100 DEG C, the response time is 0.5 24h.
8. method as claimed in claim 3, it is characterised in that step (4) described acid-base modifier is hydrochloric acid, acetic acid, three second
Amine, sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.
9. polyamic acid carried metal nanocatalyst application in preparing chemical reaction catalyst described in claim 1 or 2.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107175130A (en) * | 2017-06-12 | 2017-09-19 | 中南大学 | The stable electrum nanocatalyst of polyamic acid salt and preparation method and its application in hydramine oxidative coupling reaction |
| CN115301293A (en) * | 2022-07-15 | 2022-11-08 | 华东理工大学 | beta-CD modified polyelectrolyte stable metal nanoparticle, and preparation method and application thereof |
| CN115501917A (en) * | 2022-11-01 | 2022-12-23 | 航天科工(长沙)新材料研究院有限公司 | Nano gold catalyst and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107175130A (en) * | 2017-06-12 | 2017-09-19 | 中南大学 | The stable electrum nanocatalyst of polyamic acid salt and preparation method and its application in hydramine oxidative coupling reaction |
| CN115301293A (en) * | 2022-07-15 | 2022-11-08 | 华东理工大学 | beta-CD modified polyelectrolyte stable metal nanoparticle, and preparation method and application thereof |
| CN115501917A (en) * | 2022-11-01 | 2022-12-23 | 航天科工(长沙)新材料研究院有限公司 | Nano gold catalyst and preparation method thereof |
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